Process for producing flakes of glass

ABSTRACT

A process for producing flakes of glass. The process is started by applying a solution containing an organic metal compound to a substrate. The solution is dried and peeled from the substrate. The resultant film is sintered. There is also disclosed an apparatus for producing flakes of glass. The apparatus comprises means 2 for applying solution 1 containing an organic metal compound to a substrate 3 taking the form of a loop, means 4 for drying the film created by the solution containing the organic metal compound, and means 5 for collecting flakes obtained by peeling the dried film from the substrate. The substrate forms a circulatory continuous conveyance path which passes through the applying means, the drying means, and the collecting means in succession.

This is a division of application Ser. No. 741,496, filed Jul. 31, 1991,now U.S. Pat. No. 5,201,929.

DESCRIPTION

1. Technical Field

The present invention relates to a process for producing flakes of glassand, more particularly, to a process for producing flakes of glasseasily and efficiently, using a solution containing an organic metalcompound as the starting material.

2. Background Art

Presently, flakes of glass are used as plastic fillers, corrosionresistant linings, and paints. Such flakes of glass consist mostly ofsoda lime silicate glass and are about 4 microns in thickness. They areproduced by enlarging molten glass like a balloon, quickly cooling it,and pulverizing it. As the industry progresses, thinner flakes of glasswithstanding higher temperatures have been required. Any method ofindustrially producing flakes of glass satisfying these requirementshave not yet been put into practical use.

Naturally occurring mica is known as industrially used flakes. This hassome problems: (1) it is expensive; (2) it is colored due to impurities;and (3) it lacks durability. In spite of these problems, it has foundvarious applications, since no substitute exists.

A technique for producing sheet glass from a solution containing anorganic metal compound by the sol-gel process is described, for example,in Japanese Patent Laid-Open No. 34219/1976. In this known process, anorganic metal compound is hydrolyzed and poly-condensed. The resultantsolution is made to float on another liquid such as water, to preparesheet glass. In this described process, thin pieces of glass havingthicknesses less than 1 μm are obtained. It can be estimated that flakesof glass can be produced by pulverizing these pieces of glass. However,this technique has the following disadvantages: (1) it is difficult torecover the glass pieces floating on water; and (2) a uniform filmthickness cannot be easily obtained. Hence, it is substantiallydifficult to industrially produce flakes of glass by this technique.

DISCLOSURE OF INVENTION

In view of the foregoing prior art technique, it is an object of theinvention to provide a process and an apparatus for easily andefficiently producing thin flakes of glass which have been heretoforeimpossible to manufacture.

The novel process for producing flakes of glass uses a solutioncontaining an organic metal compound as the starting material. Thisstarting material is applied to a substrate, preferably a substratewhose surface is smooth. The starting material is then dried and peeledfrom the substrate. Subsequently, it is sintered.

In this process, the thickness of the solution containing the organicmetal compound on the substrate can be controlled by adjusting theviscosity of the solution and the concentration of the organic metalcompound in the solution. Thus, flakes of glass which have beenheretofore impossible to manufacture can be easily made.

In order to facilitate peeling the applied and dried film from thesubstrate and to easily and efficiently produce flakes of glass showingstable physical properties, the solution containing the organic metalcompound is caused to react with water. Then, the resultant solution isapplied to the substrate. Similarly, it is desired to dry, peel off, andsinter the film on the substrate. Flakes of glass which can be readilypeeled off the substrate can be obtained by this process.

An apparatus for producing flakes of glass in accordance with theinvention comprises: means for applying a solution containing an organicmetal compound to a substrate taking the form of a loop; means fordrying the film created by the solution on the substrate; and means forcollecting the flakes obtained by peeling the dried film from thesubstrate. The substrate taking the form of a loop forms a circulatorycontinuous conveyance path which passes through the applying means, thedrying means, and the collecting means in succession.

This apparatus permits flakes of glass showing stable physicalproperties to be produced in large quantities continuously andindustrially.

The flakes of glass referred to herein mean thin pieces of glass havingvertical and horizontal dimensions less than 5 mm.

BRIEF DESCRIPTION OF DRAWING

FIG. 1 is a cross-sectional view of an apparatus for producing flakes ofglass according to the invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Essentially, any organic metal compound can be used in the presentinvention as long as it can be hydrolyzed and poly-condensed, but metalalkoxides having an alkoxyl group are preferable. More specifically,methoxides, ethoxides, propoxides, butoxides, and so on of silicon,titanium, aluminum, zirconium, and other elements are used alone or incombination.

Essentially, any solvent can be used as long as a solution containing anorganic metal compound as described above is dissolved in the solvent,but the most preferred solvents are alcohols such as methanol, ethanol,propanol, and butanol. The ratio of the volume of the used solvent tothe total volume of the organic metal compound and the solvent is 0.1 to0.995, preferably 0.2 to 0.8, more preferably 0.3 to 0.75.

Water is needed for hydrolysis of the organic metal compound describedabove. This can be either acidic or basic, but in order to promote thehydrolysis, water acidified with hydrochloric acid, nitric acid,sulfuric acid, or other similar acid is preferably used. The mole ratioof the used acid to the organic metal compound is 0.01 to 2, preferably0.1 to 1.5. If a basic water is employed, the solution may be gelledeasily. In this case, the pot life of the solution is shortened.

In the case above mentioned, a solution obtained by reacting the organicmetal compound with water of a molarity of one to 100 times as high asthe molarity of the organic metal compound is preferably used. If thissolution is applied to a substrate whose surface is smooth, and if thesolution is subsequently dried, then the produced film on the substratecan be easily peeled from the substrate. Consequently, flakes of glasscan be easily and efficiently mass-produced. No specific limitations areimposed to the temperature at which the organic metal compound isreacted with the water. As an example, temperatures ranging from 10° C.to 80° C. are desired. As the hydrolysis poly-condensation progress,metalloxane bonding is produced, and high polymers grow in the solution.As the molecular weights of the high polymers increase, adhesion to thesubstrate becomes weaker, and peeling is more likely to occur.

Flakes of glass which can be peeled off more easily can be easilyproduced by applying the liquid obtained by hydrolysis andpoly-condensation of the organic metal compound to the substrate beforethe solution containing the organic metal compound is applied to thesubstrate as described above.

Preferably, the weight of the organic metal compound used per liter ofthe solution is 5 to 300 g., when converted into oxide. If theconcentration of the solution is so low that the weight of the metalcompound per liter of the solution is less than 5 g., then the film istoo thin to well peel the film from the substrate. If the concentrationis so high that the weight of the metal compound per liter of thesolution is in excess of 300 g., then the solution is gelled. This makesit impossible to industrially produce flakes of glass continuously.

To vary the characteristics of the solution, the thickness of thesolution applied to the substrate can be adjusted. For this purpose, anorganic thickener or the like may be added to the solution. However, ifthe amount of this added thickener is excessive, then the material maybe carbonized at the final stage, or heating step. Therefore, the amountof the added thickener should be limited within 10% by weight.

Where flakes of glass are produced, using the solution described above,addition of a raw material consisting of a transition metal oxide to thesolution is effective in coloring the flakes of glass. Materials forcoloring used in the present invention are compounds forming oxideswhich absorb light in the wavelength range from 400 nm to 800 nm, i.e.,transition metal compounds. No restrictions are imposed to thesematerials as long as they are substantially dissolved in the solution.Preferable materials are alkoxides, acetates, acetylacetone salts,nitrates, and chlorides of transition metals. These materials arefinally changed into oxides of transition metals within flakes of glass.The amount of the added transition metal oxide is determined by theintended coloring characteristics. Preferably, the amount of thetransition metal oxide contained in the sintered flakes of glass is inexcess of 0.1% and less than 70% , by weight. If the amount of the addedtransition metal oxide is less than 0.1% by weight, then the flakes arenot sufficiently colored. Conversely, if the amount of the addedtransition metal oxide exceeds 70 by weight, then the amount of thematrix of glass is small and so the durability of the flakes of glass isextremely low with undesirable result. Where the colored flakes of glassare employed as filler for plastics, weatherproof coloration is impartedto them.

Where flakes of glass are produced, using the above-described solution,addition of a raw material consisting of an oxide of iron, cerium,titanium, vanadium, chromium, uranium, lead, or zinc is effective inimparting the capability to absorb ultraviolet radiation to the flakesof glass. No specific limitations are placed on the material, as long asit is a compound of any of the above-described metals and substantiallydissolved in the solution. Preferred materials include alkoxides,acetates, acetylacetone salts, nitrates, and chlorides. The amount ofthe added metal oxide is determined by the intendedultraviolet-absorbing characteristics. Preferably, the amount of themetal oxide contained in the sintered flakes of glass is in excess of0.1 and less than 70% , by weight. If the amount of the added metaloxide is less than 0.1 by weight, then the flakes are not capable ofabsorbing ultraviolet radiation sufficiently. Conversely, if the amountof the added metal oxide is in excess of 70 by weight, then the amountof the matrix of glass is small. In this case, the durability of theflakes of glass is extremely low, producing undesirable result.

Where flakes of glass absorbing ultraviolet radiation are used as fillerfor plastics, the plastics are prevented from being degraded byultraviolet radiation. Also, they can be used for cosmetics blockingultraviolet light.

Where flakes of glass are produced, using the above-described solution,addition of a raw material consisting of an oxide showing electricalconduction is effective in imparting electrical conduction to the flakesof glass. In this case, the electrical conduction is imparted either byusing ions of silver oxide, sodium oxide, and lithium oxide or byelectrons of vanadium oxide, iron oxides, indium oxide, and antimonyoxide. No specific limitations are imposed to the raw materials used inthe present invention, as long as they are compounds of theabove-described metals and are substantially dissolved in the solutiondescribed above. Specific examples of the raw materials includealkoxides, acetates, acetylacetone salts, nitrates, and chlorides of themetals described above. The amount of the added metal oxide isdetermined by the intended electrical conductivity. Preferably, theamount of the metal oxide contained in the sintered flakes of glass isin excess of 0.1% and less than 70% , by weight. If the amount of theadded metal oxide is less than 0.1 by weight, then a sufficientelectrical conductivity does not appear. Conversely, if the amount ofthe added metal oxide exceeds 70% by weight, then the amount of theglass matrix is small, and the durability of the flakes of glass isextremely low with undesirable result. Where flakes of glass showingelectrical conduction are used as filler for plastics, the capability toblock or reflect electromagnetic waves can be imparted to the plastics.

The substrate used in the present invention can be made of metals,glasses, plastics whose surfaces are smooth. A liquid containing theabove-described organic metal compound is reacted with water, ifnecessary. Then, the liquid is applied to the surface of a substratemade of any of these materials. Thus, a thin film having a thickness of0.1 to 50 μm is created. The thickness of this film can be adjusted bycontrolling the viscosity of the solution. When this film dries, itshrinks, but the substrate will not shrink. Therefore, cracks areproduced in the film, giving rise to flakes. In order that the filmpeels off the substrate, it is desired that the film be not bonded tothe substrate. This requirement is fulfilled by making the substratefrom a stainless steel.

Other materials which can be preferably used to form the substrate areprecious metals such as gold and silver and materials coated with such aprecious metal.

In order to accelerate peeling of the dried film off the substrate, thefilm can be scraped off with a rotating brush or sucked by a suctionpipe.

The film can be peeled from the substrate and flakes of the film can bedispersed in water by fabricating the substrate from a plastic such aspolyimide and immersing in water the substrate to which the dried filmadheres.

The film can be formed on the substrate by a known technique. Forexample, in one method, the substrate is immersed in a solutioncontaining an organic metal compound as described above and then thesubstrate is pulled up. In another method, the solution is dripped ontothe substrate while the substrate is being spun at a high speed.

The thickness of the flakes of glass produced in accordance with thepresent invention is 0.05 to 5μm. If the thickness is greater than 5 μm,the difference in drying rate between free space and the vicinities ofthe substrate becomes too great. As a result, horizontal peeling occursbetween the films in the substrate. If this peeling takes place, thefilm thickness of the obtained flakes of glass is distributed over awide range, thus deteriorating the quality of the commercial product.Where the solution containing the organic metal compound is allowed toreact with water and then applied to the substrate, flakes of glass canbe produced up to a thickness of 10 μm. Conversely, if the thickness isless than 0.05μm, then the film adheres to the substrate too strongly,making it impossible to peel the film from the substrate. Inconsequence, flakes of glass cannot be obtained. Usually, the flakes ofglass produced in accordance with the invention lie between 10 μm andseveral millimeters in diameter.

No specific restrictions are imposed on the method of sintering.Preferably, the sintering temperature and the sintering time are soselected that the transition from gel into glass is assured. Normally,the material is heated at 300°-1200° C. for 10 minutes to 2 hours. Ifthe heating temperature and the heating time are increased,crystallization is more likely to occur. There arise no problems if thematerial is totally or partially crystallized. The word "glass" referredto herein is not limited to amorphous matter but includes crystallinematter.

The manner in which flakes of glass are produced, using theabove-described various means of the manufacturing apparatus accordingto the invention is next described.

Essentially, any means can be used to apply the solution to thesubstrate, as long as the application of the solution containing theorganic metal compound to the substrate produces a thin film. It isdesired to adopt the dipping process, i.e., the substrate is immersed inthe solution and pulled up at a constant rate.

The step of drying the film and the substrate after the application ofthe solution is carried out chiefly to evaporate the solvent. In thisstep, the film adhering to the substrate shrinks and peels off. It isdesired to heat the film to promote the evaporation. The heatingtemperature roughly lies within a range from 40° C. to 500° C. Itsuffices to heat the film for about 1 to 30 minutes. If the heatingtemperature and the heating time are increased further, no essentialimprovements are achieved; rather the thermal energy is wasted.

The step of collecting the dried flakes is carried out to gather thedried flakes on the substrate. No specific limitations are placed onthis method. Since the flakes are thin, a collection method making useof a gas is conveniently used.

In the novel apparatus, various steps can be added without trouble tothe steps using the above-described three means, i.e., the applyingmeans, the drying means, and the collecting means. For example, the stepof washing and drying the substrate is effected to completely remove theremaining flakes and other contamination just when the collection of theflakes is completed. Under this condition, the solution can be againapplied to this substrate. This is desirable from the viewpoint ofquality control. An ordinarily used washing method may be used,depending on the kind of the substrate. It is easy to; wash thesubstrate mechanically with a brush and a cleaner. Also, this washingmethod is effective.

The organic metal compound, the solvent, the moisture used for thehydrolysis, and other factors used for the novel manufacturing apparatushave been already described. It is essential that the substrate used forthe inventive manufacturing apparatus be capable of being shaped into aloop. Preferable materials which can be shaped into thin sheets and havesufficient strengths include metals such as stainless steel, aluminum,and plastics such as vinyl chloride and polyester. In any case, thesurface must be smooth. Flakes of glass having highly uniformthicknesses can be produced by feeding belts carrying the substrate at aconstant speed.

The thickness of the flakes of glass produced by the inventivemanufacturing apparatus is affected by the concentration of thesolution, the concentration of the raw material at the time of formationof the film, the drying temperature, the speed at which the substrate ismoved, and other conditions. Roughly, the thickness is between 0.05μmand 10μm. If the film thickness is greater than about 10μm, then thedifference in drying rate between the free surface on the film and thevicinities of the substrate becomes too great, thus producing horizontalpeeling between the films in the substrate. Conversely, if the filmthickness is smaller than about 0.05 μm, then the film adheres to thesubstrate too strongly. This makes it impossible to peel the film fromthe substrate. Hence, no flakes can be derived.

No specific limitations are placed on the method of sintering the peeledfilm as mentioned previously. It is required that the peeled film beheated at a sufficiently high temperate and for a sufficiently long timeto ensure that the film makes a transition from gel to glass. Specificexamples of the invention and comparative examples are given below.

EXAMPLE 1

Silicon tetraethoxide, ethanol, and water all of which were commerciallyavailable were mixed in a 1:2:1 volume ratio. The mixture was stirred atroom temperature for about 3 hours. The obtained solution having aviscosity of about 1.1 centipoises (cp) was poured onto the horizontalsurface of a sheet of stainless steel to form a thin film. The surfaceof the stainless steel sheet had been polished to make the surfacesmooth. The thickness of the sheet was 1 mm. The lamination was allowedto stand in the air and dried for about 2 hours. Then, the formed gelfilm was peeled from the stainless steel sheet. Subsequently, theobtained gel was divided into three parts. These three parts weresintered at 400° C., 600° C. 1000° C., respectively, for 1 hour. Theflakes obtained in this way had particle sizes of about 5 mm. Theseflakes were examined by X-ray diffraction. It was found that none ofthese three parts showed sharp peaks and that they were in vitreousstate. Observation of these parts with an electron microscope revealedthat they were clean glass flakes having a film thickness of 0.8μm.

EXAMPLE 2

The same solution as the solution used in Example 1 was poured ontosheet glass placed horizontally and having a thickness of 3 mm to createa thin film. The film was then dried and sintered at a temperature of400°-1000° C. for 1 hour. After the sintering, the flakes were examinedby X-ray diffraction. It was found that no sharp peaks appeared and thatthe flakes were in vitreous state. Observation of the flakes with theelectron microscope revealed that clean glass flakes having a filmthickness of 0.8 μm resulted in the same way as in Example 1.

EXAMPLE 3

First, 100 ml of silicon tetramethoxide and 100 ml of ethanol which werecommercially available were mixed. Then, 1 g. of acetylacetone salt ofiron was dissolved in the mixture. The resultant mixture was stirred atroom temperature for about 3 hours. Then, 20 ml of hydrochloric acid of0.1 normal was gradually dripped into the mixture. The resultingsolution showed a color of pale green. This solution was poured onto asheet of stainless steel to create a thin film. The surface of thestainless steel sheet had been polished to make the surface smooth. Thethickness of this sheet was 1 mm. The laminate was allowed to stand inthe air and dried. The produced gel film was peeled off and sintered attemperatures between 400° C. and 1000° C. for 1 hour. After thesintering, the flakes were investigated by X-ray diffraction. It wasfound that none of the flakes showed sharp peaks and that they were invitreous state. Chemical analysis revealed that the glass containedabout 2.5% by weight of oxides of iron.

These flakes were observed with the electron microscope. It was foundthat they were clean glass flakes having a film thickness of about 0.8μm. The flakes of glass gave a color of dark brown.

EXAMPLE 4

First, 100 ml of silicon tetramethoxide and 100 ml of ethanol which werecommercially available were mixed. Then, 109 g. of cobalt nitrate wasdissolved in the mixture. The resultant mixture was stirred at roomtemperature for about 3 hours. Thereafter, 20 ml of hydrochloric acid of0.1 normal was gradually dripped into the mixture. The resultantsolution showed a color of a very pale blue. This solution was pouredonto a stainless steel sheet and dried under the same conditions as inExample 1. The obtained flakes were sintered at temperatures between400° C. and 1000° C. for 1 hour. After the sintering, the flakes wereinvestigated by X-ray diffraction. It was found that none of the flakesshowed sharp peaks and that they were in vitreous state. Chemicalanalysis revealed that the glass contained about 68% by weight of cobaltoxide.

These flakes were observed with the electron microscope. It was foundthat they were clean glass flakes having a film thickness of about 0.8μm. These flakes of glass exhibited a color of a very deep blue.

EXAMPLE 5

This example was similar to Example 3 except that 1.0 ml of titaniumtetraisopropoxide was used instead of 1 g. of acetylacetone salt ofiron. The solution into which hydrochloric acid was dripped exhibited acolor of a pale yellow. After the sintering, the resultant flakes wereanalyzed chemically. It was found that the glass contained about 6% byweight of titanium oxide.

The glass flakes were observed with the electron microscope. They werevery clean glass flakes having a film thickness of about 0.8 μm.Measurement of the transmittance characteristics showed that anabsorption end existed at 280 nm and that rapid absorption was exhibitedat the ultraviolet wavelengths.

EXAMPLE 6

This example was similar to Example 3 except that 20 g. of hydrated zincnitrate (Zn(NO₃)₂. 6H₂ O) was used instead of 1 g. of acetylacetone saltof iron. The solution into which hydrochloric acid was dripped wasalmost colorless and transparent. After the sintering of the gel film,it was analyzed chemically. The glass contained about 11% by weight ofzinc oxide.

The glass flakes were observed with the electron microscope. It wasfound that they were clean glass flakes having a film thickness of about0.8 μm. Measurement of the transmittance characteristics showed that anabsorption end existed at 300 nm and that rapid absorption was exhibitedat the ultraviolet wavelengths.

EXAMPLE 7

This example was similar to Example 3 except that 6.5 ml oftriisopropoxy vanadyl was used instead of 1 g. of acetylacetone salt ofiron. After sintering the gel film, it was chemically analyzed. Theglass contained about 9.5% by weight of vanadium oxides.

The glass was observed with the electron microscope. It was found thatclean flakes of glass having a film thickness of about 0.8 μm wereproduced. These glass flakes were mixed with a commercially availableepoxy resin in a 1:10 weight ratio. The resultant mixture was stretchedup to a thickness of about 2 mm on a glass plate and solidified. Theresultant film was peeled off, and an electrical resistance between twolocations which were spaced apart 10 cm was measured. The resistance wasabout 100 ohms. Since the epoxy resin alone did not show electricalconduction, it was confirmed that the flakes of glass had a highelectrical conductivity.

EXAMPLE 8

This example was similar to Example 3 except that 10 g. of metal sodiumwas employed instead of 1 g. of acetylacetone salt of iron. After thesintering of the gel film, it was analyzed chemically. The glasscontained about 32% by weight of sodium oxide. It was observed with theelectron microscope. Clean flakes of glass having a film thickness ofabout 0.8μm were observed. The flakes of glass were mixed with an epoxyresin to fabricate a composite film, and an electrical resistancebetween the two points spaced apart 10 cm was measured, in the same wayas in Example 7. The resistance was about 500 ohms. It was proved thatthe flakes of glass had a high electrical conductivity.

EXAMPLE 9

Silicon tetraethoxide, ethanol, and hydrochloric acid water of 0.1normal all of which were commercially available were mixed in a 1:2:1volume ratio. At this time, the added water was about 8 times as much asthe silicon tetraethoxide in terms of molar ratio. The concentration ofsilica was about 100 g. per liter of the solution. The mixture wasstirred at 40° C. for about 20 hours. The resultant solution was pouredonto a stainless steel sheet of 1 mm thickness to create a thin film.The surface of the stainless steel sheet had been polished to smoothenthe surface. The film was allowed to stand in the air and dried. Thefilm peeled from the substrate over the whole area of the appliedsolution, producing flakes. The flakes were sintered at temperaturesbetween 400° C. and 1000° C. for 1 hour. After the sintering, the flakeswere examined by X-ray diffraction. None of the flakes showed sharppeaks. They were in vitreous state. They were observed with the electronmicroscope. We noticed clean flakes of glass having a film thickness of0.8 μm.

EXAMPLE 10

Silicon tetraethoxide, ethanol, and hydrochloric acid water of 0.1normal all of which were commercially available were mixed in a 4:0.5:1volume ratio. The added water was about 2 times as much as the silicontetraethoxide in terms of molar ratio. The concentration of silica wasabout 290 g. per liter of the solution. The reaction was carried outunder the same conditions as in Example 9. The resultant solution waspoured onto a glass sheet having a thickness of 3 mm and dried. At thistime, the film peeled off the substrate over the whole area of theapplied solution, thus giving rise to flakes. The flakes were sinteredat temperatures between 400° C. and 1000° C. for 1 hour. After thesintering, the flakes were investigated by X-ray diffraction. None ofthe flakes showed sharp peaks. They were in vitreous state. Observationwith the electron microscope revealed that they were clean flakes ofglass having a film thickness of 1.5μm.

EXAMPLE 11

Silicon tetraethoxide and pure water which were commercially availablewere mixed in a 1:12 volume ratio. At this time, the added water wasabout 98 times as much as the silicon tetraethoxide in terms of molarratio. The concentration of silica was about 30 g. per liter of thesolution. The reaction was carried out under the same conditions as inExample 9. The solution was poured onto a glass sheet having a thicknessof 3 mm and dried. At this time, the film peeled off the substrate overthe whole area of the applied solution, resulting in flakes.

The flakes were sintered at temperatures between 400° C. and 1000° C.for 1 hour. After the sintering, the flakes were investigated by X-raydiffraction. None of the flakes showed sharp peaks. They were invitreous state. Observation with the electron microscope revealed thatthey were clean flakes of glass having a film thickness of 0.5μm.

COMPARATIVE EXAMPLE 1

The water of the solution in Example 9 described above was replaced withethanol. A solution was prepared by mixing 1 part by volume of silicontetraethoxide with 3 parts by volume of ethanol both of which werecommercially available. This solution was not hydrolyzed norpolymerized. This solution was applied to a stainless steel substrateand dried under the same conditions as in Example 9. Then, peeling wasattempted. During the drying, about 90 of the total area of the filmdisappeared due to evaporation. The remaining 10% of the film adheredstrongly to the substrate, and it was difficult to peel off theremaining film.

EXAMPLE 12

An apparatus for producing flakes of glass is shown in FIG. 1. Solution1 was prepared by mixing 1000 ml of silicon tetramethoxide and 1000 mlof ethanol, and 1200ml of hydrochloric acid of 0.1 normal all of whichwere commercially available. This solution 1 was contained in a bath tub2. A substrate 3 to which solution 1 was to be applied was a stainlesssteel belt having a width of 30 cm and a thickness of 50 μm. This beltwas fed at a constant speed of 50 cm/min. to produce flakescontinuously. A film was created on the substrate just at the instantthat the substrate 3 was pulled into the air out of solution 1. Dryingwas effected by passing the substrate 3 through an electric furnace 4that was retained at 80° C. At this time, flakes of glass were peeledfrom the substrate 3. At the same time, the flakes were collected by adevice 5 that sucked them over the substrate 3. The collected flakeswere heated at 800° C. by an electric furnace (not shown) to produceflakes of glass. The substrate 3 was washed and dried by a brush 6rotating in a direction opposite to the direction of movement of thesubstrate. A device 7 for spraying pure water was mounted to enhance theeffect of the washing. The drying was performed with a hot air drier 8.After going through these steps, the substrate 3 was placed in theoriginal position. This apparatus could produce flakes of glasscontinuously.

It is to be noted that FIG. 1 shows only one example of the inventivemanufacturing apparatus and that the invention is not limited to thisexample.

Industrial Applicability

In accordance with the inventive method, very thin flakes of glass, verythin colored flakes of glass, very thin flakes of glass absorbingultraviolet radiation, and very thin flakes of glass showing electricalconduction which have been heretofore difficult to produce can be easilyand efficiently produced.

Also, in the inventive apparatus, flakes of glass which have beenheretofore difficult to produce can be continuously, easily, andefficiently produced.

I claim:
 1. A process for producing amorphous or crystalline flakesabsorbing ultraviolet radiation, comprising,preparing an organic siliconcompound, an alcohol for solving the organic silicon compound, acompound effective in imparting capability to absorb ultravioletradiation, said compound being soluble to the alcohol in which theorganic silicon compound is solved and containing a material selectedfrom the group consisting of iron, cerium, titanium, vanadium, chromium,uranium, lead and zinc, and water for hydrolysis of the organic siliconcompound, mixing the organic silicon compound, alcohol, compound forabsorption of ultraviolet radiation and water together so thathydrolysis of the organic silicon compound occurs and polymerscontaining said material for absorption of ultraviolet radiation grow tothereby form a solution, applying the solution onto a substrate, dryingthe solution on the substrate to form a film containing the material forabsorption of ultraviolet radiation and silicon, said film, whiledrying, shrinking and cracking on the substrate to thereby form flakes,and heat-treating the flakes to form the amorphous or crystallineflakes, 0.1-70 wt % of an oxide with said material for absorption ofultraviolet radiation being included in the flakes.
 2. The process ofclaim 1, wherein the amount of the organic silicon compound contained inthe solution is 5 to 300 grams per liter of the solution when calculatedas silicon oxide.
 3. The process of claim 1, wherein the organic metalcompound is silicon alkoxide having an alkoxyl group.
 4. The process ofclaim 1, wherein the ratio of the volume of the solvent to the totalvolume of the organic silicon compound and the solvent is 0.1 to 0.995.5. The process of claim 1, wherein said water is an acidic water.
 6. Theprocess of claim 5, wherein the mole ratio of the acid water to theorganic silicon compound is 0.01 to
 2. 7. The process of claim 1,wherein the hydrolysis occurs at a temperature of 10°-80° C.
 8. Theprocess of claim 1, wherein the solution containing the organic siliconcompound is applied to the substrate for a thickness of 0.1 to 50 μm. 9.The process of claim 1, wherein said substrate is made of stainlesssteel.
 10. The process of claim 1, wherein the heat-treating isperformed at 300°-1200° C. for 10 minutes to 2 hours.
 11. The processaccording to claim 1, wherein in said mixing, 1 mole of the organicsilicon compound is mixed with 1-100 moles of water to react the organicsilicon compound with water, said solution containing metalloxanebonding formed by hydrolysis of the organic silicon compound, saidamorphous or crystalline flake having a thickness between 0.05 and 10micrometer and a diameter between 10 micrometer and several millimeters.12. The process according to claim 1, wherein said substrate is in aform of a loop and is rotated endlessly to continuously form the flakes.13. The process according to claim 12, further comprising collecting theflakes from the substrate for the sintering, and washing and drying thesubstrate so that the flakes are continuously formed while the substrateis endlessly moving.
 14. The process according to claim 1, wherein saidflakes are added to cosmetics for blocking ultraviolet light.
 15. Aprocess for producing amorphous or crystalline flakes absorbingultraviolet radiation, comprising,mixing an organic metal compound, analcohol for solving the organic metal compound, and a compound effectivein imparting capability to absorb ultraviolet radiation, said compoundfor absorption of ultraviolet radiation being soluble to the alcohol inwhich the organic metal compound is solved and containing a materialselected from the group consisting of iron, cerium, titanium, vanadium,chromium, uranium, lead and zinc, adding water to the above mixturecontaining the organic metal compound, alcohol and compound forabsorption of ultraviolet radiation so that hydrolysis of the organicmetal compound occurs and polymers containing said material forabsorption of ultraviolet radiation grow in a solution, applying thesolution onto a substrate, drying the solution on the substrate to forma film containing the metal compound and the material for absorption ofultraviolet radiation, said film, while drying, shrinking and crackingon the substrate to thereby form flakes, and heat-treating the flakes toform the amorphous or crystalline flakes.
 16. The process according toclaim 15, wherein 0.1-70 wt % of an oxide with said material forabsorption of ultraviolet radiation is included in the flakes, 1 mole ofthe organic metal compound being mixed with 1-100 moles of water in saidmixing, said solution containing metalloxane bonding formed byhydrolysis of the organic metal compound, said amorphous or crystallineflake having a thickness between 0.05 and 10 micrometer and a diameterbetween 10 micrometer and several millimeters.